Integrating atomic scale processes: ald (atomic layer deposition) and ale (atomic layer etch)

ABSTRACT

Methods are provided for integrating atomic layer etch and atomic layer deposition by performing both processes in the same chamber or reactor. Methods involve sequentially alternating between atomic layer etch and atomic layer deposition processes to prevent feature degradation during etch, improve selectivity, and encapsulate sensitive layers of a semiconductor substrate.

INCORPORATION BY REFERENCE

An Application Data Sheet is filed concurrently with this specificationas part of the present application. Each application that the presentapplication claims benefit of or priority to as identified in theconcurrently filed Application Data Sheet is incorporated by referenceherein in their entireties and for all purposes.

BACKGROUND

As feature sizes shrink, there is a growing need for atomic scaleprocessing such as Atomic Layer Deposition (ALD) and Atomic Layer Etch(ALE). ALD and ALE processes are conventionally performed as separateprocesses, such that all ALD or all ALE operations are performed beforeall ALE or all ALD operations, respectively. Conventional ALD and ALEprocesses use separate reactors or chambers to accommodate conditions,precursor chemistry, and parameters for each corresponding process.

SUMMARY

Provided are methods of integrating atomic layer etch and atomic layerdeposition. One aspect involves a method of processing a substrate byetching the substrate by atomic layer etch in a chamber; and depositinga film by atomic layer deposition in the chamber, whereby the etchingand the depositing are performed without breaking vacuum.

The etching may be performed in cycles, where a cycle includes: exposinga substrate to an etching gas to modify the surface of the substrate;and exposing the substrate to a removal gas to remove at least some ofthe modified surface. Exposing the substrate to the etching gas mayfurther include igniting a plasma. In some embodiments, the methodfurther includes applying a bias to the substrate. The etching gas maybe a chlorine-containing compound. In various embodiments, a cycleetches between about 1 Å to about 50 Å of film. The chamber may bepurged between exposures.

The depositing may be performed in cycles, where a cycle includes:exposing the substrate to a deposition precursor to modify the surfaceof the substrate; and exposing the substrate to a reducing agent todeposit the film. In some embodiments, the method further includesigniting a plasma. In some embodiments, at least some of the depositionprecursor adsorbs onto the surface of the substrate during the exposingof the substrate to the deposition precursor. The chamber may be purgedbetween exposures.

In some embodiments, the etching and the depositing are performed todeposit material on the substrate. In some embodiments, the etching andthe depositing are performed to etch material on the substrate.

In various embodiments, the etching further includes directionallysputtering the substrate. In some embodiments, the etching and thedepositing is performed in the same chamber. The etching may beperformed nonconformally. In some embodiments, at least one of theetching or the depositing is a self-limiting reaction.

Another aspect involves a method including: (a) exposing a substratehoused in a chamber to alternating pulses of an etching gas and aremoval gas to etch the substrate layer by layer; (b) exposing thesubstrate to alternating pulses of a first reactant and a secondreactant to deposit a film over the substrate; and (c) repeating (a) and(b) in the same chamber.

The removal gas may be a carrier gas selected from the group consistingof N₂, Ar, He, and Ne. In some embodiments, (a) and (b) are performed inthe same chamber and are performed sequentially. Furthermore, thechamber may be purged between pulses. In various embodiments, (a)further includes applying a bias to the substrate. In some embodiments,(a) further includes directionally sputtering the substrate.

In some embodiments, the method also includes igniting a plasma whenexposing the substrate to the removal gas. The method may also includeigniting a plasma when exposing the substrate to the second reactant.

In various embodiments, at least one of (a) or (b) is a self-limitingreaction. In some embodiments, (a) and (b) are repeated to depositmaterial on the substrate. In some embodiments, (a) and (b) are repeatedto etch a film on the substrate. In various embodiments, the substrateis selected from the group consisting of metals and dielectrics.

Another aspect involves an apparatus for processing substrates, theapparatus including: one or more process chambers, each process chamberincluding a chuck; one or more gas inlets into the process chambers andassociated flow-control hardware; and a controller having at least oneprocessor and a memory, whereby the at least one processor and thememory are communicatively connected with one another, the at least oneprocessor is at least operatively connected with the flow-controlhardware, and the memory stores computer-executable instructions forcontrolling the at least one processor to at least control theflow-control hardware by etching the substrate by atomic layer etch in achamber; and depositing a film by atomic layer deposition in thechamber, whereby etching and depositing are performed without breakingvacuum.

Another aspect involves an apparatus for processing substrates, theapparatus including: one or more process chambers, each process chamberincluding a chuck; one or more gas inlets into the process chambers andassociated flow-control hardware; and a controller having at least oneprocessor and a memory, whereby the at least one processor and thememory are communicatively connected with one another, the at least oneprocessor is at least operatively connected with the flow-controlhardware, and the memory stores computer-executable instructions forcontrolling the at least one processor to at least control theflow-control hardware by: (a) exposing a substrate to alternating pulsesof an etchant and purge gas to etch the substrate layer by layer; (b)exposing the substrate to alternating pulses of a reducing agent and aprecursor to deposit a film on the etched substrate; and (c) repeating(a) and (b) without breaking vacuum between performing (a) and (b).

These and other aspects are described further below with reference tothe drawings.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1A is a process flow diagram depicting operations for a method inaccordance with disclosed embodiments.

FIG. 1B is a schematic illustration of examples of etch and deposition.

FIG. 1C is a process flow diagram depicting operations for a method inaccordance with disclosed embodiments.

FIG. 1D is a timing schematic diagram depicting an example of operationsperformed in accordance with disclosed embodiments.

FIG. 2 is a schematic diagram of an example process chamber forperforming disclosed embodiments.

FIG. 3 is a schematic diagram of an example process apparatus forperforming disclosed embodiments.

FIG. 4 shows images of an etched substrate from an experiment conductedin accordance with disclosed embodiments.

DETAILED DESCRIPTION

In the following description, numerous specific details are set forth toprovide a thorough understanding of the presented embodiments. Thedisclosed embodiments may be practiced without some or all of thesespecific details. In other instances, well-known process operations havenot been described in detail to not unnecessarily obscure the disclosedembodiments. While the disclosed embodiments will be described inconjunction with the specific embodiments, it will be understood that itis not intended to limit the disclosed embodiments.

As feature sizes shrink, there is a growing need for atomic scaleprocessing such as Atomic Layer Deposition (ALD) and Atomic Layer Etch(ALE). These are cyclic processes of nominally self-limiting steps thatresult in digital and small changes in film thicknesses. The processesare characterized by smoothness and conformality, and alsodirectionality in the case of some ALE. The ALD and ALE processes havebeen conventionally performed independently such that all depositionprocesses are performed before all etch processes, or vice versa.Conventional ALD and ALE processes are performed on different tools. Forexample, conventionally ALD tools do not run ALE processes, and ALEtools do not run ALD processes.

Provided herein are methods for integrating etching and depositionprocesses in situ (e.g., in the same chamber of a tool or withoutbreaking vacuum). The disclosed embodiments may be used fornet-depositing material or net-etching material on a substrate. Somemethods described herein involve depositing a passivation layer by ALDduring ALE processes. Disclosed methods are suitable for a wide range ofapplications, including etching processes for trenches and holes,fabrication of MRAM, fabrication of phase change materials, improvedselectivity in etching processes, and poly dummy removal. For example,deposition during etch may be used to protect sidewalls or a mask duringetch or encapsulate a material during etch and with subsequent exposureto atmosphere, or provide selectivity if the deposition is selective;and etching during deposition may be used to keep features open duringdeposition.

FIG. 1A provides a process flow diagram for performing operations in amethod in accordance with disclosed embodiments. Operations in FIG. 1Amay be performed at a chamber pressure between about 1 mTorr and about100 Torr, e.g., about 1 mTorr and about 1 Torr. In operation 101, asubstrate or wafer is provided to a processing chamber. The chamber maybe a chamber in a multi-chamber apparatus or a single-chamber apparatus.The substrate may be a silicon wafer, e.g., a 200-mm wafer, a 300-mmwafer, or a 450-mm wafer, including wafers having one or more layers ofmaterial, such as dielectric, conducting, or semi-conducting materialdeposited thereon. In some embodiments, the substrate includes a blanketlayer of silicon, such as amorphous silicon, or a blanket layer ofgermanium. The substrate may include a patterned mask layer previouslydeposited and patterned on the substrate. For example, a mask layer maybe deposited and patterned on a substrate including a blanket amorphoussilicon layer.

In some embodiments, the layers on the substrate may be patterned.Substrates may have “features” such as via or contact holes, which maybe characterized by one or more of narrow and/or re-entrant openings,constrictions within the feature, and high aspect ratios. The featuremay be formed in one or more of the above described layers. One exampleof a feature is a hole or via in a semiconductor substrate or a layer onthe substrate. Another example is a trench in a substrate or layer. Invarious embodiments, the feature may have an under-layer, such as abarrier layer or adhesion layer. Non-limiting examples of under-layersinclude dielectric layers and conducting layers, e.g., silicon oxides,silicon nitrides, silicon carbides, metal oxides, metal nitrides, metalcarbides, and metal layers.

In some embodiments, the features may have aspect ratios of at leastabout 2:1, at least about 4:1, at least about 6:1, at least about 10:1,at least about 30:1, or higher. Protection of feature sidewalls may bedesirable at high aspect ratios. Disclosed methods may be performed onsubstrates with features having an opening less than about 150 nm. Afeature via or trench may be referred to as an unfilled feature or afeature. A feature that may have a re-entrant profile that narrows fromthe bottom, closed end, or interior of the feature to the featureopening. In some embodiments, the methods described herein may be usedto form features having these characteristics.

Returning to FIG. 1A, in operation 103, the substrate is etched by ALEin the chamber. ALE is a technique that removes thin layers of materialusing sequential self-limiting reactions. Generally, ALE may beperformed using any suitable technique. Examples of atomic layer etchtechniques are described in U.S. Pat. No. 8,883,028, issued on Nov. 11,2014; and U.S. Pat. No. 8,808,561, issued on Aug. 19, 2014, which areherein incorporated by reference for purposes of describing exampleatomic layer etch and etching techniques. In various embodiments, ALEmay be performed with plasma, or may be performed thermally.

Operation 103 may be performed in cycles. The concept of an “ALE cycle”is relevant to the discussion of various embodiments herein. Generallyan ALE cycle is the minimum set of operations used to perform an etchprocess one time, such as etching a monolayer. The result of one cycleis that at least some of a film layer on a substrate surface is etched.Typically, an ALE cycle includes a modification operation to form areactive layer, followed by a removal operation to remove or etch onlythis modified layer. The cycle may include certain ancillary operationssuch as sweeping one of the reactants or byproducts. Generally, a cyclecontains one instance of a unique sequence of operations. As an example,an ALE cycle may include the following operations: (i) delivery of areactant gas, (ii) purging of the reactant gas from the chamber, (iii)delivery of a removal gas and an optional plasma, and (iv) purging ofthe chamber. In some embodiments, etching may be performednonconformally. FIG. 1B shows two example schematic illustrations of anALE cycle. Diagrams 171 a-171 e show a generic ALE cycle. In 171 a, thesubstrate is provided. In 171 b, the surface of the substrate ismodified. In 171 c, the next step is prepared. In 171 d, the modifiedlayer is being etched. In 171 e, the modified layer is removed.Similarly, diagrams 172 a-172 e show an example of an ALE cycle foretching a silicon film. In 172 a, a silicon substrate is provided, whichincludes many silicon atoms. In 172 b, reactant gas chlorine isintroduced to the substrate which modifies the surface of the substrate.The schematic in 172 b shows that some chlorine is adsorbed onto thesurface of the substrate as an example. Although chlorine is depicted inFIG. 1B, any chlorine-containing compound or suitable reactant may beused. In 172 c, the reactant gas chlorine is purged from the chamber. In172 d, a removal gas argon is introduced with a directional plasma asindicated by the Ar⁺ plasma species and arrows, and ion bombardment isperformed to remove the modified surface of the substrate. During thisoperation, a bias is applied to the substrate to attract ions toward it.In 172 e, the chamber is purged and the byproducts are removed.

A cycle may only partially etch about 0.1 nm to about 50 nm of material,or between about 0.1 nm and about 5 nm of material, or between about 0.2nm and about 50 nm of material, or between about 0.2 nm and about 5 nmof material. The amount of material etched in a cycle may depend on thepurpose of integrating with ALD. For example, if ALD is integrated toprotect the sidewalls, then the amount etched in ALE cycles may bevaried such that performing ALD protects the exposed sidewalls at thebottom of the feature. In some embodiments, a cycle of ALE may removeless than a monolayer of material.

Etching chemistry is introduced into the chamber in operation 103 ofFIG. 1A. As described herein, in operations where materials areintroduced into the chamber, in some embodiments involving atomic layeretch using a plasma, the reactor or chamber may be stabilized byintroducing the chemistry into the chamber prior to processing thesubstrate or wafer. Stabilizing the chamber may use the same flow rates,pressure, temperatures, and other conditions as the chemistry to be usedin the operation following the stabilization. In some embodiments,stabilizing the chamber may involve different parameters. In someembodiments, a carrier gas, such as N₂, Ar, Ne, He, and combinationsthereof, is continuously flowed during operation 103. In someembodiments, a carrier gas is only used during removal. The carrier gasmay be used as a purge gas in some operations as described below. Insome embodiments, another reactant gas, such as oxygen, is used duringoperation 103 to remove a modified layer. In some embodiments, a carriergas is not flowed during removal.

Provided herein is an example of modification and removal operationsthat may be performed in operation 103. The modification operation formsa thin, reactive surface layer with a thickness that is more easilyremoved than the un-modified material in the subsequent removaloperation. In a modification operation, a substrate may be chlorinatedby introducing chlorine into the chamber. Chlorine is used as an exampleetchant species in disclosed embodiments, but it will be understood thatin some embodiments, a different etching gas is introduced into thechamber. The etching gas may be selected depending on the type andchemistry of the substrate to be etched. In some embodiments, a plasmamay be ignited and chlorine reacts with the substrate for the etchingprocess. In some embodiments, chlorine may react with the substrate ormay be adsorbed onto the surface of the substrate. In variousembodiments, chlorine is introduced into the chamber in a gaseous formand may be optionally accompanied by a carrier gas which may be any ofthose described above. The species generated from a chlorine plasma canbe generated directly by forming a plasma in the process chamber housingthe substrate or they can be generated remotely in a process chamberthat does not house the substrate, and can be supplied into the processchamber housing the substrate. In some embodiments, a plasma is not usedand chlorine may be introduced thermally into the chamber.

In various embodiments, the plasma may be an inductively coupled plasmaor a capacitively coupled plasma. An inductively coupled plasma may beset at a plasma between about 50 W and about 2000 W. In someembodiments, a bias may be applied between about 0V and about 500V.

In some embodiments, a purge may be performed after a modificationoperation. In a purge operation, non-surface-bound active chlorinespecies may be removed from the process chamber. This can be done bypurging and/or evacuating the process chamber to remove the activespecies, without removing the adsorbed layer. The species generated in achlorine plasma can be removed by simply stopping the plasma andallowing the remaining species decay, optionally combined with purgingand/or evacuation of the chamber. Purging can be done using any inertgas such as N₂, Ar, Ne, He and their combinations.

In a removal operation, the substrate may be exposed to an energy source(e.g. activating or sputtering gas or chemically reactive species thatinduces removal), such as argon or helium, to etch the substrate bydirectional sputtering. In some embodiments, the removal operation maybe performed by ion bombardment. During removal, a bias may beoptionally turned on to facilitate directional sputtering. In someembodiments, ALE may be isotropic.

The amount of sputtering gas may be controlled such as to etch only atargeted amount of material. In various embodiments, the pressure of thechamber may vary between the modification and removal operations. Thepressure of the gas may depend on the size of the chamber, the flow rateof the gas, the temperature of the reactor, the type of substrate, andthe size of substrate to be etched. If the bias is turned on duringremoval, the bias may be set at about 50 eV for etching features,trenches, or holes in a soft material such as amorphous silicon. In someembodiments, the chamber may be purged after a removal operation. Purgeprocesses may be any of those used for a purge after a modificationoperation.

In various embodiments, the modification and removal operations may berepeated in cycles, such as about 1 to about 30 cycles, or about 1 toabout 20 cycles. Any suitable number of ALE cycles may be included toetch a desired amount of film. In some embodiments, ALE is performed incycles to etch about 1 Å to about 50 Å of the surface of the layers onthe substrate. In some embodiments, cycles of ALE etch between about 2 Åand about 50 Å of the surface of the layers on the substrate.

Returning to FIG. 1A, in operation 105, a thin film is deposited on thesubstrate by ALD in the same chamber where the substrate was etched inoperation 103 or without breaking vacuum from operation 103. Operations103 and 105 may be performed in situ, or in a vacuum, without an airbreak or without breaking vacuum. In various embodiments, asilicon-containing film is deposited in operation 105. Examplesilicon-containing films include silicon oxide and silicon oxynitrideand silicon nitride. In some embodiments, a metal or metal-containingfilm may be deposited. In some embodiments operation 105 may beperformed prior to operation 103. In some embodiments operation 103 maybe performed prior to operation 105.

ALD is a technique that deposits thin layers of material usingsequential self-limiting reactions. ALD may be performed using anysuitable technique. In various embodiments, ALD may be performed withplasma, or may be performed thermally. Operation 105 may be performed incycles.

The concept of an “ALD cycle” is relevant to the discussion of variousembodiments herein. Generally an ALD cycle is the minimum set ofoperations used to perform a surface deposition reaction one time. Theresult of one cycle is production of at least a partialsilicon-containing film layer on a substrate surface. Typically, an ALDcycle includes operations to deliver and adsorb at least one reactant tothe substrate surface, and then react the adsorbed reactant with one ormore reactants to form the partial layer of film. The cycle may includecertain ancillary operations such as sweeping one of the reactants orbyproducts and/or treating the partial film as deposited. Generally, acycle contains one instance of a unique sequence of operations. As anexample, an ALD cycle may include the following operations: (i)delivery/adsorption of a silicon-containing precursor, (ii) purging ofsilicon-containing precursor from the chamber, (iii) delivery of asecond reactant and a plasma, and (iv) purging of plasma from thechamber.

FIG. 1B shows an example schematic illustration of an ALD cycle fordepositing silicon oxide (SiO₂). Diagrams 182 a-182 e show a generic ALDcycle. In 182 a, a silicon substrate is provided, which includes manysilicon atoms. In 182 b, oxygen is introduced to the substrate as oxygenradicals, which modify the surface of the substrate. This may be thedelivery of the reactant and plasma. Note some oxygen radicals areadsorbed onto the surface of the substrate as an example. In 182 c, theoxygen radicals are purged from the chamber. In 182 d, asilicon-containing precursor or silicon source is introduced and thesilicon source reacts with the oxygen radicals adsorbed on the surfaceof the substrate. In 182 e, the chamber is purged and the byproducts areremoved, leaving behind a deposited layer of SiO₂.

In some embodiments, the films deposited by ALD may be highly conformal.Conformality of films may be measured by the step coverage. Stepcoverage may be calculated by comparing the average thickness of adeposited film on a bottom, sidewall, or top of a feature to the averagethickness of a deposited film on a bottom, sidewall, or top of afeature. For example, step coverage may be calculated by dividing theaverage thickness of the deposited film on the sidewall by the averagethickness of the deposited film at the top of the feature andmultiplying it by 100 to obtain a percentage.

Unlike a chemical vapor deposition (CVD) technique, ALD processes usesurface-mediated deposition reactions to deposit films on alayer-by-layer basis. In one example of an ALD process, a substratesurface, including a population of surface active sites, is exposed to agas phase distribution of a first precursor, such as asilicon-containing precursor, in a dose provided to a process chamberhousing the substrate. Molecules of this first precursor are adsorbedonto the substrate surface, including chemisorbed species and/orphysisorbed molecules of the first precursor. It should be understoodthat when the compound is adsorbed onto the substrate surface asdescribed herein, the adsorbed layer may include the compound as well asderivatives of the compound. For example, an adsorbed layer of asilicon-containing precursor may include the silicon-containingprecursor as well as derivatives of the silicon-containing precursor. Incertain embodiments, an ALD precursor dose partially saturates thesubstrate surface. In some embodiments, the dose phase of an ALD cycleconcludes before precursor contacts the substrate to evenly saturate thesurface. Typically, the precursor flow is turned off or diverted at thispoint, and only purge gas flows. By operating in this sub-saturationregime, the ALD process reduces the cycle time and increases throughput.However, because precursor adsorption is not saturation limited, theadsorbed precursor concentration may vary slightly across the substratesurface. Examples of ALD processes operating in the sub-saturationregime are provided in U.S. patent application Ser. No. 14/061,587,filed Oct. 23, 2013, titled “SUB-SATURATED ATOMIC LAYER DEPOSITION ANDCONFORMAL FILM DEPOSITION,” which is incorporated herein by reference inits entirety. After a first precursor dose, the reactor is thenevacuated to remove any first precursor remaining in gas phase so thatonly the adsorbed species remain. A second reactant, such as an oxygenor nitrogen-containing gas, is introduced to the reactor so that some ofthese molecules react with the first precursor adsorbed on the surface.In some processes, the second precursor reacts immediately with theadsorbed first precursor. In other embodiments, the second precursorreacts only after a source of activation is applied temporally. Thereactor may then be evacuated again to remove unbound second precursormolecules. Additional ALD cycles may be used to build film thickness.

In some implementations, the ALD methods include plasma activation, suchas when the second reactant is delivered to a chamber. As describedherein, the ALD method and apparatuses described herein may be conformalfilm deposition (CFD) methods, which are described generally in U.S.patent application Ser. No. 13/084,399 (now U.S. Pat. No. 8,728,956),filed Apr. 11, 2011, and titled “PLASMA ACTIVATED CONFORMAL FILMDEPOSITION,” and in U.S. patent application Ser. No. 13/084,305, filedApr. 11, 2011, and titled “SILICON NITRIDE FILMS AND METHODS,” which areherein incorporated by reference in its entireties. Additional examplesof ALD processes are described in Puurunen, “Surface chemistry of atomiclayer deposition: for the trimethylaluminum/water process”, 97 J.Applied Physics 12301 (2005), which is herein incorporated by referencefor the purpose of providing description for suitable ALD processes.

Returning to FIG. 1A, in operation 105, in some embodiments, a carriergas, such as N₂, Ar, Ne, He, and combinations thereof, may becontinuously flowed. The carrier gas may be used as a purge gas. Theinert gas may be provided to assist with pressure and/or temperaturecontrol of the process chamber, evaporation of a liquid reactant, morerapid delivery of the reactant and/or as a sweep gas for removingprocess gases from the process chamber and/or process chamber plumbing.

Provided herein is an example of adsorption and second reactant deliveryoperations that may be performed in operation 105. In an adsorptionoperation of an ALD cycle, the substrate may be exposed to a filmprecursor, such as silicon tetrachloride (SiCl₄), to adsorb onto thesubstrate surface. In some embodiments, the film precursor may be asilicon-containing precursor. In some embodiments, the film precursor,such as SiCl₄, may be adsorbed onto about 60% of the substrate surface.In various embodiments, when the film precursor is flowed to thechamber, the film precursor adsorbs onto active sites on the surface ofthe substrate, forming a thin layer of the film precursor on thesurface. In various embodiments, this layer may be less than amonolayer.

After adsorption, the chamber may be optionally purged to remove excessprecursor in gas phase that did not adsorb onto the surface of thesubstrate. Purging may involve a sweep gas, which may be a carrier gasused in other operations or a different gas. In some embodiments,purging may involve evacuating the chamber.

In a second reactant delivery operation of an ALD cycle, the substratemay be exposed to a second reactant and, optionally, a plasma. Invarious embodiments, the second reactant is oxygen (O₂) or nitrogen (N₂)or combinations thereof. In some embodiments where a silicon oxide layeris deposited, oxygen is used as the second reactant. In someembodiments, second reactant flow and the plasma are both turned on. Insome embodiments, second reactant flow may be turned on prior to turningon the plasma to, for example, allow the second reactant flow tostabilize.

In some embodiments, the optional plasma is an in-situ plasma, such thatthe plasma is formed directly above the substrate surface in thechamber. In various embodiments, the plasma may be an inductivelycoupled plasma or a capacitively coupled plasma. A inductively coupledplasma may be set at a plasma between about 50 W and about 2000 W. Insome embodiments, a bias may be applied between about 0V and about 500V.During delivery of the second reactant, the film precursor, such asSiCl₄, is turned off. The substrate may be exposed to the secondreactant and the optional plasma for a duration that exceeds a time forplasma to interact with all precursors adsorbed on the substratesurface, forming a continuous film atop the substrate surface.

After the second reactant delivery operation, the chamber may be purged,such as by introducing a carrier or inert gas. Conditions for thisoperation may be any of those described above for purge processes.

In various embodiments, ALD cycles may be repeated. For example,operations for ALD may be performed for about 5 to about 70 cycles. Anysuitable number of deposition cycles may be included to deposit adesired film thickness of the deposited film. In some embodiments, anALD cycle may deposit about 1 Å per cycle. Depending on the exposuretime of the operations, each cycle may deposit a film, such as a siliconoxide or silicon oxynitride film, having a thickness between about 0.05Å and about 5 Å. In some embodiments, about two to about three cycles ofALD may be performed per minute. In some embodiments, more than aboutthree cycles may be performed per minute, such as in chambers withinlets positioned to be closer to the substrate.

In some embodiments, ALD operations produce conformal films capable ofprotecting the features from lateral etching in subsequent ALEprocesses, which may occur in the same chamber. In some embodiments, ALDis integrated to selectively deposit films on a substrate, such as todeposit films on corners of a feature to protect them from erosionduring etching processes. In some embodiments, at least one of operation103 and 105 is self-limiting reaction. In some embodiments, at least oneof operation 103 and 105 is as self-limiting reaction as possible. Forexample, in some embodiments, only operation 103 is a self-limitingprocess. In some embodiments, only operation 105 is a self-limitingprocess. In some embodiments, both operations 103 and 105 areself-limiting. In various embodiments, operations 103 and 105 may beperformed sequentially. Examples of sequentially performing theseoperations are further described below with respect to FIGS. 1C and 1D.

In operation 107, a bias is optionally applied. Applying a bias may etchsidewalls, so in various embodiments, a bias may not appliedcontinuously and may be applied after various cycles of ALD and ALE.This operation may be performed to break through the film deposited byALD. In some embodiments, the bias is set to about 80 eV to breakthrough the layer deposited by cycles of ALD.

In operation 109, it is determined whether sufficient etching has beenperformed. If the profile is not sufficiently etched, operations 103-109may be repeated. In some embodiments operations 103-109 are performed inthe same chamber or without breaking vacuum for the repeated cycles asin the initial cycle.

FIG. 1C and 1D provide further examples of disclosed embodiments. Inoperation 110, a substrate housed in a chamber may be exposed to anetchant or etching gas to modify the surface of the substrate. This maybe referred to as a “surface modification” operation. In someembodiments, this may correspond to the surface modification phase 150Ashown in FIG. 1D and may be part of an etch cycle. As shown in FIG. 1D,during this operation, a carrier gas may be optionally flowed, while anetchant is flowed to the chamber. A carrier gas may be any of thecarrier gases described above with respect to FIG. 1A. In someembodiments, a carrier gas is not flowed during surface modification.The etchant may be flowed such that it modifies only the top surface ofthe substrate. In various embodiments, a bias may be applied duringoperation 110. The bias may be applied at a power between about 0V andabout 500V.

Returning to FIG. 1C, in operation 112, the modified layer of thesubstrate may be removed from the substrate by exposing the substrate toa sputtering gas in a removal operation, which may be the same as ordifferent from a carrier gas. In various embodiments, at least part ofthe substrate surface may be etched in this operation. The exampleprovided above with respect to operation 103 may be used in accordancewith these operations. Performing operations 110 and 112 may, in someembodiments, constitute performing atomic layer etch once. In someembodiments, operations 110 and 112 may be optionally repeated one ormore times (e.g., in one or more cycles).

Operation 112 may correspond to the removal phase 152A as shown in FIG.1D. Performing the surface modification 150A and removal 152A mayconstitute an etch cycle 130A. In some embodiments, a cycle may includemore operations. During removal, a carrier gas may be flowed withoutflowing any other chemistry. The carrier gas may be flowed to helpfacilitate purging of the modified layer as it is etched. The exampleprovided in FIG. 1D is an example of performing operation 110 of FIG. 1Cand operation 112 one time without repeating operations 110 and 112.

In operation 114, the substrate is exposed to a first reactant to adsorbthe first reactant onto at least some of the substrate surface. Thisoperation may be performed without breaking vacuum from performingoperations 110 and 112. In some embodiments, the first reactant is afilm precursor as described herein. In various embodiments, the firstreactant may adsorb onto active sites of the substrate. The abovedescribed examples of adsorption during an ALD cycle are relevant tothis operation.

Operation 114 may correspond to first precursor exposure phase 164A ofFIG. 1D. During this operation, the first precursor may be flowed withan optional carrier gas. Note that during this operation, the etchantflow and second reactant flow to be described further below may not beflowed. This operation may be performed for a duration sufficient tosaturate at least part of the surface of the substrate. In someembodiments, at least about 40%, or at least about 60%, or at leastabout 80%, or about 100% of the surface may be saturated.

In some embodiments, after performing the first precursor exposure phase164A, the chamber housing the substrate may be optionally purged inpurge phase 165A in FIG. 1D. During the purge phase 165A, a carrier gasis flowed to remove excess first precursor that did not adsorb onto thesurface of the substrate. In some embodiments, the purge phase is notperformed.

Returning to FIG. 1C, operation 116 may be performed such that thesubstrate is exposed to a second reactant. In various embodiments, thesecond reactant may be a reducing agent. The second reactant reacts withthe adsorbed layer to deposit a thin film on the substrate. Note that insome embodiments, operations 114 and 116 may be performed in reversesuch that operation 116 is performed prior to adsorbing the firstreactant onto the surface of the substrate. Operation 116 may correspondto second reactant exposure phase 166A as shown in FIG. 1D. During thisphase, the second reactant is flowed, and a carrier gas is optionallyflowed. In some embodiments, a second reactant is flowed without acarrier gas. The etchant and first precursor flow are not turned onduring this phase. In various embodiments, the second reactant exposurephase may also include igniting a plasma (not shown). In someembodiments the thin layer of film may be deposited without use of aplasma. In some embodiments, the chamber is optionally purged after thesecond reactant exposure phase 166A during purge phase 167A. The purgephase 167A may be performed to remove byproducts or excess secondreactant in gas phase from the chamber. In some embodiments, the chamberis not purged.

Operations 114 and 116 of FIG. 1C may be optionally repeated one or moretimes. Performing operations 114 and 116 may constitute an ALD cycle asdescribed above with respect to FIG. 1A. In various embodiments,operations 110-116 are repeated one or more times. A combination ofrepeated cycles of operations 110 and 112, and repeated cycles ofoperations 114 and 116 may be performed in further cycles. For example,in some embodiments, a cycle including performing operations 110-112twice, and performing operations 114-116 three times, may be repeatedtwo or more times. In some embodiments, cycles of operations 110-112 andoperations 114-116 are performed sequentially. For example, afterperforming operations 110-112, operations 114-116 are performed, and/orvice versa. The frequency of cycles and the number of cycles used in aprocess may depend on the type of application disclosed embodiments areused for.

In FIG. 1D, each cycle is repeated once. As such, etch cycle 130Aconstitutes repeating operations 110-112 of FIG. 1C once, depositioncycle 132A constitutes repeating operations 114-116 of FIG. 1C once, andboth cycles are then repeated once more in etch cycle 130B anddeposition cycle 132B. Etch cycle 130B includes a surface modificationphase 150B and a removal phase 152B, while deposition cycle 132Bincludes a first precursor exposure phase 164B, purge phase 165B, secondreactant exposure phase 166B, and purge phase 167B. Note that in someembodiments, further repeated cycles may or may not include purge phases165B and 167B. In some embodiments, durations of exposures and purgephases may vary from cycle to cycle during an integrated process. Insome embodiments, the number of cycles may change over time during anetch integrated process.

In some embodiments, the carrier gas may only be flowed during the etchcycles and not the deposition cycles. In some embodiments, the carriergas may only be flowed during deposition cycles and not the etch cycles.In some embodiments, carrier gases may vary between etch and depositioncycles.

In various embodiments, process conditions, such as pedestaltemperature, chamber temperature, chamber pressure, gas flow rates, gasflow chemistry, duration of pulses, exposures, and purges, plasmafrequency, plasma power, and bias power, may be adjusted depending onthe type of application and the type of apparatus or tool upon which thedisclosed embodiments are implemented.

Methods described herein may be suitable for various applications.Examples of applications include: (1) high aspect ratio sidewall or maskprotection, (2) MRAM (magnetoresistive random access memory) etching andencapsulation processes, and (3) selectivity improvement duringdirectional etch processes.

In some semiconductor processes, soft materials, such as amorphoussilicon or germanium, are directionally etched to form trenches orholes, or substrates with layers having such features in it may beexposed to directional etching. However, some neutral species may formin the trench or feature which may etch sidewalls of the features. AnALE process in small features in particular may cause sidewalls to besusceptible to lateral etching that may elongate the features. Methodsdescribed herein by integrating ALE and ALD processes, the filmdeposited during ALD may protect the sidewalls of these features frombeing etched during ALE. Likewise, these ALE and ALD integratedprocesses may be used to reduce corner faceting in masks, improverigidity of a mask, and prevent degradation of a mask.

Conventional MRAM etching and encapsulation processes often involveexposing a moisture-sensitive layer, thereby risking contamination ofthe device. Although encapsulation is used in MRAM fabrication,encapsulation as described herein may also be used for other devicefabrication and may be used for other sensitive layers.

In MRAM etching, an MRAM stack may include a tantalum mask deposited onan MTJ (magnetic tunnel junction), which is further deposited on acobalt and/or tantalum layer, and a substrate. In some embodiments,there are more layers deposited between these layers. An MTJ may includetwo cobalt iron boron (CoFeB) layers, with a magnesium oxide (MgO) layersandwiched between the two CoFeB layers.

This stack may be etched by first etching the ruthenium layer. In someembodiments, the tantalum layer may be etched by ALE. Subsequently, anargon or helium plasma may be used to etch and open the MTJ, therebyexposing a moisture-sensitive layer. Methods described herein allow thesubstrate to remain in the same chamber while ALD is then performed todeposit a thin encapsulation film over the moisture-sensitive layer andencapsulate it. In some embodiments, this thin encapsulation film is anoxide or nitride layer. In various embodiments, the cobalt and/ortantalum layer below may then be etched to break through to thesubstrate to continue etching the layer below.

Methods described herein may also be suitable for improving selectivityin etch processes. For example, in some embodiments, conformal layerdeposition may be performed to deposit thicker layers on some surfacesof the substrate. In some embodiments, selective ALD may be performed todeposit a thin film on some areas and not on others, such thatsubsequent ALE processes etch the exposed areas more than theALD-deposited areas. For example, ALD may be performed to deposit onedges of features to prevent them from faceting during ALE.

Apparatus

Inductively coupled plasma (ICP) reactors which, in certain embodiments,may be suitable for atomic layer etching (ALE) operations and atomiclayer deposition (ALD) operations are now described. Such ICP reactorshave also described in U.S. Patent Application Publication No.2014/0170853, filed Dec. 10, 2013, and titled “IMAGE REVERSAL WITH AHMGAP FILL FOR MULTIPLE PATTERNING,” hereby incorporated by reference inits entirety and for all purposes. Although ICP reactors are describedherein, in some embodiments, it should be understood that capacitivelycoupled plasma reactors may also be used.

FIG. 2 schematically shows a cross-sectional view of an inductivelycoupled plasma integrated etching and deposition apparatus 200appropriate for implementing certain embodiments herein, an example ofwhich is a Kiyo™ reactor, produced by Lam Research Corp. of Fremont,Calif. The inductively coupled plasma apparatus 200 includes an overallprocess chamber 201 structurally defined by chamber walls 201 and awindow 211. The chamber walls 201 may be fabricated from stainless steelor aluminum. The window 211 may be fabricated from quartz or otherdielectric material. An optional internal plasma grid 250 divides theoverall processing chamber 201 into an upper sub-chamber 202 and a lowersub-chamber 203. In most embodiments, plasma grid 250 may be removed,thereby utilizing a chamber space made of sub-chambers 202 and 203. Achuck 217 is positioned within the lower sub-chamber 203 near the bottominner surface. The chuck 217 is configured to receive and hold asemiconductor wafer 219 upon which the etching and deposition processesare performed. The chuck 217 can be an electrostatic chuck forsupporting the wafer 219 when present. In some embodiments, an edge ring(not shown) surrounds chuck 217, and has an upper surface that isapproximately planar with a top surface of a wafer 219, when presentover chuck 217. The chuck 217 also includes electrostatic electrodes forchucking and dechucking the wafer. A filter and DC clamp power supply(not shown) may be provided for this purpose. Other control systems forlifting the wafer 219 off the chuck 217 can also be provided. The chuck217 can be electrically charged using an RF power supply 223. The RFpower supply 223 is connected to matching circuitry 221 through aconnection 227. The matching circuitry 221 is connected to the chuck 217through a connection 225. In this manner, the RF power supply 223 isconnected to the chuck 217.

Elements for plasma generation include a coil 233 is positioned abovewindow 211. In some embodiments, a coil is not used in disclosedembodiments. The coil 233 is fabricated from an electrically conductivematerial and includes at least one complete turn. The example of a coil233 shown in FIG. 2 includes three turns. The cross-sections of coil 233are shown with symbols, and coils having an “X” extend rotationally intothe page, while coils having a “●” extend rotationally out of the page.Elements for plasma generation also include an RF power supply 241configured to supply RF power to the coil 233. In general, the RF powersupply 241 is connected to matching circuitry 239 through a connection245. The matching circuitry 239 is connected to the coil 233 through aconnection 243. In this manner, the RF power supply 241 is connected tothe coil 233. An optional Faraday shield 249 is positioned between thecoil 233 and the window 211. The Faraday shield 249 is maintained in aspaced apart relationship relative to the coil 233. The Faraday shield249 is disposed immediately above the window 211. The coil 233, theFaraday shield 249, and the window 211 are each configured to besubstantially parallel to one another. The Faraday shield may preventmetal or other species from depositing on the dielectric window of theplasma chamber 201.

Process gases (e.g. chlorine, argon, silicon tetrachloride, oxygen,nitrogen, etc.) may be flowed into the processing chamber 201 throughone or more main gas flow inlets 260 positioned in the upper chamber 202and/or through one or more side gas flow inlets 270 Likewise, though notexplicitly shown, similar gas flow inlets may be used to supply processgases to a capacitively coupled plasma processing chamber. A vacuumpump, e.g., a one or two stage mechanical dry pump and/or turbomolecularpump 240, may be used to draw process gases out of the process chamber201 and to maintain a pressure within the process chamber 201. Forexample, the pump may be used to evacuate the chamber 201 during a purgeoperation of ALD. A valve-controlled conduit may be used to fluidicallyconnect the vacuum pump to the processing chamber 201 so as toselectively control application of the vacuum environment provided bythe vacuum pump. This may be done employing a closed-loop-controlledflow restriction device, such as a throttle valve (not shown) or apendulum valve (not shown), during operational plasma processing.Likewise, a vacuum pump and valve controlled fluidic connection to thecapacitively coupled plasma processing chamber may also be employed.

During operation of the apparatus, one or more process gases may besupplied through the gas flow inlets 260 and/or 270. In certainembodiments, process gas may be supplied only through the main gas flowinlet 260, or only through the side gas flow inlet 270. In some cases,the gas flow inlets shown in the figure may be replaced more complex gasflow inlets, one or more showerheads, for example. The Faraday shield249 and/or optional grid 250 may include internal channels and holesthat allow delivery of process gases to the chamber 201. Either or bothof Faraday shield 249 and optional grid 250 may serve as a showerheadfor delivery of process gases. In some embodiments, a liquidvaporization and delivery system may be situated upstream of the chamber201, such that once a liquid reactant or precursor is vaporized, thevaporized reactant or precursor is introduced into the chamber 201 via agas flow inlet 260 and/or 270. Example liquid precursors include SiCl₄and silicon amides.

Radio frequency power is supplied from the RF power supply 241 to thecoil 233 to cause an RF current to flow through the coil 233. The RFcurrent flowing through the coil 233 generates an electromagnetic fieldabout the coil 233. The electromagnetic field generates an inductivecurrent within the upper sub-chamber 202. The physical and chemicalinteractions of various generated ions and radicals with the wafer 219selectively etch features of and deposit layers on the wafer.

If the plasma grid is used such that there is both an upper sub-chamber202 and a lower sub-chamber 203, the inductive current acts on the gaspresent in the upper sub-chamber 202 to generate an electron-ion plasmain the upper sub-chamber 202. The optional internal plasma grid 250limits the amount of hot electrons in the lower sub-chamber 203. In someembodiments, the apparatus is designed and operated such that the plasmapresent in the lower sub-chamber 203 is an ion-ion plasma.

Both the upper electron-ion plasma and the lower ion-ion plasma maycontain positive and negative ions, though the ion-ion plasma will havea greater ratio of negative ions to positive ions. Volatile etchingand/or deposition byproducts may be removed from the lower-sub-chamber203 through port 222. The chuck 217 disclosed herein may operate atelevated temperatures ranging between about 10° C. and about 250° C. Thetemperature will depend on the process operation and specific recipe.

Chamber 201 may be coupled to facilities (not shown) when installed in aclean room or a fabrication facility. Facilities include plumbing thatprovide processing gases, vacuum, temperature control, and environmentalparticle control. These facilities are coupled to chamber 201, wheninstalled in the target fabrication facility. Additionally, chamber 201may be coupled to a transfer chamber that allows robotics to transfersemiconductor wafers into and out of chamber 201 using typicalautomation.

In some embodiments, a system controller 230 (which may include one ormore physical or logical controllers) controls some or all of theoperations of a processing chamber. The system controller 230 mayinclude one or more memory devices and one or more processors. In someembodiments, the apparatus includes a switching system for controllingflow rates and durations when disclosed embodiments are performed. Insome embodiments, the apparatus may have a switching time of up to about5 00 ms, or up to about 7 50 ms. Switching time may depend on the flowchemistry, recipe chosen, reactor architecture, and other factors.

In some implementations, a controller 230 is part of a system, which maybe part of the above-described examples. Such systems can comprisesemiconductor processing equipment, including a processing tool ortools, chamber or chambers, a platform or platforms for processing,and/or specific processing components (a wafer pedestal, a gas flowsystem, etc.). These systems may be integrated with electronics forcontrolling their operation before, during, and after processing of asemiconductor wafer or substrate. The electronics may be referred to asthe “controller,” which may control various components or subparts ofthe system or systems. The controller 230, depending on the processingparameters and/or the type of system, may be programmed to control anyof the processes disclosed herein, including the delivery of processinggases, temperature settings (e.g., heating and/or cooling), pressuresettings, vacuum settings, power settings, radio frequency (RF)generator settings, RF matching circuit settings, frequency settings,flow rate settings, fluid delivery settings, positional and operationsettings, wafer transfers into and out of a tool and other transfertools and/or load locks connected to or interfaced with a specificsystem.

Broadly speaking, the controller 230 may be defined as electronicshaving various integrated circuits, logic, memory, and/or software thatreceive instructions, issue instructions, control operation, enablecleaning operations, enable endpoint measurements, and the like. Theintegrated circuits may include chips in the form of firmware that storeprogram instructions, digital signal processors (DSPs), chips defined asapplication specific integrated circuits (ASICs), and/or one or moremicroprocessors, or microcontrollers that execute program instructions(e.g., software). Program instructions may be instructions communicatedto the controller in the form of various individual settings (or programfiles), defining operational parameters for carrying out a particularprocess on or for a semiconductor wafer or to a system. The operationalparameters may, in some embodiments, be part of a recipe defined byprocess engineers to accomplish one or more processing steps during thefabrication of one or more layers, materials, metals, oxides, silicon,silicon dioxide, surfaces, circuits, and/or dies of a wafer.

The controller 230, in some implementations, may be a part of or coupledto a computer that is integrated with, coupled to the system, otherwisenetworked to the system, or a combination thereof. For example, thecontroller may be in the “cloud” or all or a part of a fab host computersystem, which can allow for remote access of the wafer processing. Thecomputer may enable remote access to the system to monitor currentprogress of fabrication operations, examine a history of pastfabrication operations, examine trends or performance metrics from aplurality of fabrication operations, to change parameters of currentprocessing, to set processing steps to follow a current processing, orto start a new process. In some examples, a remote computer (e.g. aserver) can provide process recipes to a system over a network, whichmay include a local network or the Internet. The remote computer mayinclude a user interface that enables entry or programming of parametersand/or settings, which are then communicated to the system from theremote computer. In some examples, the controller 230 receivesinstructions in the form of data, which specify parameters for each ofthe processing steps to be performed during one or more operations. Itshould be understood that the parameters may be specific to the type ofprocess to be performed and the type of tool that the controller isconfigured to interface with or control. Thus as described above, thecontroller 230 may be distributed, such as by comprising one or morediscrete controllers that are networked together and working towards acommon purpose, such as the processes and controls described herein. Anexample of a distributed controller for such purposes would be one ormore integrated circuits on a chamber in communication with one or moreintegrated circuits located remotely (such as at the platform level oras part of a remote computer) that combine to control a process on thechamber.

Without limitation, example systems may include a plasma etch chamber ormodule, a deposition chamber or module, a spin-rinse chamber or module,a metal plating chamber or module, a clean chamber or module, a beveledge etch chamber or module, a physical vapor deposition (PVD) chamberor module, a chemical vapor deposition (CVD) chamber or module, an ALDchamber or module, an ALE chamber or module, an ion implantation chamberor module, a track chamber or module, and any other semiconductorprocessing systems that may be associated or used in the fabricationand/or manufacturing of semiconductor wafers.

As noted above, depending on the process step or steps to be performedby the tool, the controller might communicate with one or more of othertool circuits or modules, other tool components, cluster tools, othertool interfaces, adjacent tools, neighboring tools, tools locatedthroughout a factory, a main computer, another controller, or tools usedin material transport that bring containers of wafers to and from toollocations and/or load ports in a semiconductor manufacturing factory.

FIG. 3 depicts a semiconductor process cluster architecture with variousmodules that interface with a vacuum transfer module 338 (VTM). Thearrangement of transfer modules to “transfer” wafers among multiplestorage facilities and processing modules may be referred to as a“cluster tool architecture” system. Airlock 330, also known as aloadlock or transfer module, is shown in VTM 338 with four processingmodules 320 a-320 d, which may be individual optimized to performvarious fabrication processes. By way of example, processing modules 320a-320 d may be implemented to perform substrate etching, deposition, ionimplantation, wafer cleaning, sputtering, and/or other semiconductorprocesses. In some embodiments, ALD and ALE are performed in the samemodule. In some embodiments, ALD and ALE are performed in differentmodules of the same tool. One or more of the substrate etchingprocessing modules (any of 320 a-320 d) may be implemented as disclosedherein, i.e., for depositing conformal films, selectively depositingfilms by ALD, etching patterns, and other suitable functions inaccordance with the disclosed embodiments. Airlock 330 and processmodule 320 may be referred to as “stations.” Each station has a facet336 that interfaces the station to VTM 338. Inside each facet, sensors1-18 are used to detect the passing of wafer 326 when moved betweenrespective stations.

Robot 322 transfers wafer 326 between stations. In one embodiment, robot322 has one arm, and in another embodiment, robot 322 has two arms,where each arm has an end effector 324 to pick wafers such as wafer 326for transport. Front-end robot 332, in atmospheric transfer module (ATM)340, is used to transfer wafers 326 from cassette or Front OpeningUnified Pod (FOUP) 334 in Load Port Module (LPM) 342 to airlock 330.Module center 328 inside process module 320 is one location for placingwafer 326. Aligner 344 in ATM 340 is used to align wafers.

In an exemplary processing method, a wafer is placed in one of the FOUPs334 in the LPM 342. Front-end robot 332 transfers the wafer from theFOUP 334 to an aligner 344, which allows the wafer 326 to be properlycentered before it is etched or processed. After being aligned, thewafer 326 is moved by the front-end robot 332 into an airlock 330.Because airlock modules have the ability to match the environmentbetween an ATM and a VTM, the wafer 326 is able to move between the twopressure environments without being damaged. From the airlock module330, the wafer 326 is moved by robot 322 through VTM 338 and into one ofthe process modules 320 a-320 d. In order to achieve this wafermovement, the robot 322 uses end effectors 324 on each of its arms. Oncethe wafer 326 has been processed, it is moved by robot 322 from theprocess modules 320 a-320 d to an airlock module 330. From here, thewafer 326 may be moved by the front-end robot 332 to one of the FOUPs334 or to the aligner 344.

It should be noted that the computer controlling the wafer movement canbe local to the cluster architecture, or can be located external to thecluster architecture in the manufacturing floor, or in a remote locationand connected to the cluster architecture via a network. A controller asdescribed above with respect to FIG. 2 may be implemented with the toolin FIG. 3.

Experimental Experiment 1

An experiment was conducted in accordance with disclosed embodiments. Anamorphous silicon substrate was provided. The substrate also included apatterned mask. The substrate was provided into a Kiyo™ reactoravailable from Lam Research Corp., of Fremont, Calif. The substrate wasexposed to 50 cycles of ALE to etch features. After the cycles of ALE,the substrate was then exposed to 50 cycles of ALD to generate 5 nm ofSiO₂ using SiCl₄ as a precursor and O₂ plasma as a second reactant inthe same Kiyo reactor without breaking vacuum. Note that 5 nm of SiO₂was deposited to visibly show a result in the image of the substrate.

The resulting etched features in the substrate 400 are depicted in FIG.4. Image 401 shows the etched substrate with the patterned mask 410,with a conformal blanket layer of SiO₂ 420 deposited over the patternedmask 410. Note that in the image shown, a capping layer of chromium 430is shown. Image 403 shows an enlarged image of the same features inimage 401. As shown in image 403, the SiO₂ 420 deposited by ALD isconformal with about 5 nm on the sidewalls, and about 5.4 nm depositedat the bottom of the features. The results demonstrate the viability ofan integrated ALE and ALD process in the same chamber.

CONCLUSION

Although the foregoing embodiments have been described in some detailfor purposes of clarity of understanding, it will be apparent thatcertain changes and modifications may be practiced within the scope ofthe appended claims. It should be noted that there are many alternativeways of implementing the processes, systems, and apparatus of thepresent embodiments. Accordingly, the present embodiments are to beconsidered as illustrative and not restrictive, and the embodiments arenot to be limited to the details given herein.

1-31. (canceled)
 32. A method comprising: providing a substrate to a chamber, the substrate having a feature with an aspect ratio of at least about 2:1; exposing the substrate to alternating pulses of an etching gas and a removal gas to etch the substrate layer by layer; and exposing the substrate to alternating pulses of a first reactant and a second reactant to deposit a film over the substrate.
 33. The method of claim 32, wherein a plasma is ignited during at least one of a pulse of the etching gas and a pulse of the removal gas.
 34. The method of claim 32, wherein the aspect ratio is at least about 4:1.
 35. The method of claim 32, wherein the aspect ratio is at least about 6:1.
 36. The method of claim 32, wherein the aspect ratio is at least about 10:1.
 37. The method of claim 32, wherein the aspect ratio is at least about 30:1.
 38. The method of claim 32, wherein a pulse of the etching gas modifies the substrate to form a modified material and a pulse of the removal gas removes at least some of the modified material.
 39. The method of claim 32, wherein etching the substrate layer by layer is performed in a self-limiting manner.
 40. The method of claim 32, wherein depositing the film over the substrate is performed in a self-limiting manner.
 41. The method of claim 32, wherein exposing the substrate to the alternating pulses of the etching gas and the removal gas comprises applying a bias to the substrate.
 42. The method of claim 41, wherein the bias is applied during the pulses of the removal gas but not during the pulses of the etching gas.
 43. The method of claim 32, wherein the exposing the substrate to the alternating pulses of the etching gas and the removal gas and the exposing the substrate to the alternating pulses of the first reactant and the second reactant are performed without breaking vacuum.
 44. A method comprising: providing a substrate to a chamber, the substrate having a feature with a feature opening of less than about 150 nm; exposing the substrate to alternating pulses of an etching gas and a removal gas to etch the substrate layer by layer; and exposing the substrate to alternating pulses of a first reactant and a second reactant to deposit a film over the substrate.
 45. The method of claim 44, wherein a plasma is ignited during at least one of a pulse of the etching gas and a pulse of the removal gas.
 46. The method of claim 44, wherein a pulse of the etching gas modifies the substrate to form a modified material and a pulse of the removal gas removes at least some of the modified material.
 47. The method of claim 44, wherein etching the substrate layer by layer is performed in a self-limiting manner.
 48. The method of claim 44, wherein depositing the film over the substrate is performed in a self-limiting manner.
 49. The method of claim 44, wherein exposing the substrate to the alternating pulses of the etching gas and the removal gas comprises applying a bias to the substrate.
 50. The method of claim 49, wherein the bias is applied during the pulses of the removal gas but not during the pulses of the etching gas.
 51. The method of claim 44, wherein the exposing the substrate to the alternating pulses of the etching gas and the removal gas and the exposing the substrate to the alternating pulses of the first reactant and the second reactant are performed without breaking vacuum. 